Meta-bis anilide derivatives and their utility as herbicides

ABSTRACT

Compounds corresponding to the formula: ##SPC1## 
     In which R 1  and R 2  are, independently, hydrogen, alkyl, alkoxyalkyl, cycloalkyl, pinonyl, ethylcycloalkyl, lower alkenyl, halogenated lower alkyl, benzyl, ethylphenyl, 2,4-dichlorophenoxy-methylene, styryl, furyl, phenyl or substituted phenyl in which the substituents are nitro, halogen, methyl, or methoxy; R 3  and R 4  are, independently, hydrogen or lower alkyl; X and Y are independently oxygen or sulfur; and Z is halogen, nitro, amino, lower alkyl, lower alkoxy or trifluoromethyl and n is an integer having a value from 0 to 4. The above compounds are effective herbicides, particularly for the control of grasses and broadleaf plants with both pre-emergence and post-emergence activity. Representative compounds are: m-propionamidobutyranilide, m-bis-2,2-dimethylvaleranilide, m-isobutyramido trichloroacetanilide, m-isobutyramido-2-ethylbutyranilide, m-t-butylacetamidopropionanilide, and 3&#39;-N-ethyl propionamido-propionalide. 
     This application is a continuation of application Ser. No. 180,916, filed Sept. 15, 1971, which is a continuation of application Ser. No. 20,104, filed Mar. 16, 1970, which is a continuation-in-part of application Ser. No. 741,267, filed July 1, 1968, which is a continuation-in-part of application Ser. No. 659,865, filed Aug. 11, 1967, all now abandoned.

This invention relates to herbicidally active meta-bis anilide derivatives. More specifically, this invention relates to certain new compounds and the use as active herbicidal substances of certain substituted meta-bis-anilides.

The novel compounds of the present invention correspond to the general formula: ##SPC2##

In which R₁ and R₂ are independently selected from the group consisting of hydrogen, alkyl, alkoxyalkyl, cycloalkyl, pinonoyl, ethylcycloalkyl, lower alkenyl, halogenated lower alkyl, benzyl, furyl, ethylphenyl, 2,4-dichlorophenoxy-methylene, styryl, phenyl, and substituted-phenyl in which said substituents are nitro, halogen, methyl or methoxy; selected from the group consisting of hydrogen and lower alkyl; X and Y are independently oxygen or sulfur; and Z is selected from the group consisting of halogen, nitro, amino, lower alkyl, lower alkoxy, and trifluoromethyl and n is an integer having a value from 0 to 4.

The method of the present invention of controlling undesirable vegetation comprises applying an herbicidally effective amount of the above represented compounds to the area where control is desired. Compounds wherein R₁ and R₂ are independently selected from the group consisting of alkyl, hydrogen, alkoxyalkyl, cycloalkyl, pinonoyl, ethylcycloalkyl, lower alkenyl, halogenated lower alkyl, benzyl, 2,4-dichlorophenoxymethylene, styryl, phenyl, phenyl and substituted phenyl in which the substituents are nitro, halogen, methyl or methoxy; R₃ and R₄ are independently selected from the group consisting of hydrogen and lower alkyl; X and Y are independently oxygen or sulfur; and Z is selected from the group consisting of halogen, nitro, amino, lower alkyl, lower alkoxy, and trifluoromethyl and n is an integer having a value from 0 to 4; are within the scope of this aspect of the present invention.

The term alkyl, preferably includes those members of the group which contains from 1 through about 10 carbon atoms, inclusive, in both straight chain and branched chain configurations. The term lower alkyl and lower alkoxy preferably include members of the groups having from 1 through about 6 carbon atoms, inclusive. The term alkoxyalkyl includes members having 2 to 4 carbon atoms. The term cycloalkyl preferably includes members of the group having from 3 through about 6 carbon atoms, inclusive. The term lower alkenyl preferably includes those members of the group containing at least one double bond and containing from 2 to 4 carbon atoms, inclusive.

In its most preferred form, the invention relates to compositions having the formula ##SPC3##

in which R₁ and R₂ independently are hydrogen, alkyl containing from 1 to 10 carbon atoms, inclusive, alkoxyalkyl containing 2 to 4 carbon atoms, cycloalkyl containing from 3 to 6 carbon atoms, inclusive, pinonoyl, ethylcycloalkyl wherein the cycloalkyl moiety contains from 5 to 6 carbon atoms, inclusive, lower alkenyl containing from 2 to 6 carbon atoms, inclusive, halogenated lower alkyl containing 1 to 6 carbon atoms, inclusive, benzyl, furyl, ethylphenyl, styryl, 2,4-dichlorophenoxy-methylene, phenyl and substituted phenyl in which said substituents are nitro, halogen, especially chlorine and fluorine, methyl, and methoxy; and Z is hydrogen, 4'-chloro, 3'-chloro or 2'-methyl.

The compounds of this invention are prepared by one of several general methods. One such general method is the condensation between the appropriate m-phenylene diamine and an appropriate acid anhydride or chloride to prepare the desired meta-bis-symmetrically substituted anilide. Another general method is the condensation between the appropriate m-mono-substituted amino anilide and an appropriate acide anhydride or acid chloride to prepare the desired meta-bis-assymetrically substituted anilide. The reactions proceed readily in the liquid phase. The employment of a solvent is also useful, facilitating processing, as well as agitation of the reactants. When using a starting material containing an acid chloride, it is preferred to carry out the reaction in the presence of a hydrogen halide acceptor such as triethylamine, pyridine, picoline, sodium carbonate and the like. The reactions are preferably carried out at temperatures that permit operation in the liquid phase.

Compounds of the present invention are prepared in accordance with the following illustrative examples.

EXAMPLE 1 Preparation of Meta-bis-isobutyranilide

Isobutyric anhydride, 26g. (0.16 mole) is added slowly to 8.6g. (0.08 mole) of m-phenylene diamine in an open beaker. The mixture was stirred. The solid product is washed consecutively with water, sodium bicarbonate solution and ether. After drying, there is obtained 18.5g. (92 percent of theory) of the title compound, m.p. 205°-206°C.

The following compounds are typical of those prepared using the method of the foregoing example: m-bis-acetanilide, m-bis-propionanilide, m-bis-n-butyranilide and m-bis-trifluoroacetanilide.

EXAMPLE 2 Preparation of Meta-bis-2,2-dimethyl-valeranilide

Meta-phenylene diamine, 87g. (0.8 moles), is dissolved in one liter of acetone containing 190g. (1.9 moles) of triethylamine. To this solution, 2,2-dimethylvaleryl chloride, 260g. (1.75 moles) is added slowly with stirring. The reaction flask is cooled in a cold water bath. The resulting mixture is poured into 1-liter of cold water and the resulting oil crystallized. The product is further washed with water, then 5 percent hydrochloric acid solution, followed by 5 percent sodium hydroxide solution and finally water. The product is dried. There is obtained 256g. (96 percent of theory) of the title compound, m.p. 109°-111°C.

The following compounds are typical of those prepared using the method of the foregoing example: m-bis-pivalanilide, m-bis-3,3-dimethylbutyranilide, m-bis-crotonanilide, m-bis-hexanilide, and m-bis-isovalerylanilide.

EXAMPLE 3 Preparation of Meta-propionamido isobutyranilide

Meta-amino propionanilide, 11.5g. (0.07 moles) is treated with isobutyric anhydride, 11.1g. (0.07 moles) is an open beaker. The product is poured into water and washed with 5 percent hydrochloric acid solution, 5 percent sodium hydroxide solution, and water. The product is dried of water. There is obtained 15.2g. (93 percent of theory) of the title compound, m.p. 174°-175°C.

The following compounds are typical of those prepared using the method of the foregoing example: m-propionamido trifluoroacetanilide, m-propionamido butyranilide, m-isobutyramido trifluoroacetanilide and m-isobutyramido butyranilide.

EXAMPLE 4 Preparation of Meta-propionamido cyclopropane carboxanilide

Meta-aminopropionanilide, 13.1g. (0.08 mole) is dissolved in 200 ml. of a 50/50 v/v mixture of glacial acetic acid and saturated sodium acetate solution. To this solution is added 9.2g. (0.088 moles) of cyclopropane carbonyl chloride. The chloride is added slowly with adequate stirring and cooling. The product, which crystallizes from the solution, is collected by filtration. The product is consecutively washed with a 5 percent solution of sodium hydroxide, a 5 percent solution of hydrochloric acid and water. After washing, the crystals are dried. There is obtained 15g. (81 percent of theory) of the title compound, m.p. 185°-186°C.

The following compounds are typical of those prepared using the method of the foregoing example: m-propionamido cyclohexanecarboxanilide, m-propionamido phenyl-acetanilide, m-propionamido crotonanilide, and m-propionamido furoanilide.

EXAMPLE 5 Preparation of Meta-propionamido-3,3-dimethyl butylanilide

Meta-aminopropionanilide, 180g. (1.1 moles) is dissolved in 500 ml. of acetone containing 126g. of triethylamine. To this solution is added 164g. (1.22 moles) of 3,3-dimethyl butyryl chloride. The chloride is added slowly and the reaction mixture is adequately stirred and cooled, with an ice bath. The mixture is poured into water and consecutively washed with 5 percent hydrochloric acid solution, 5 percent sodium hydroxide solution, and water. After washing, the material is dried. There is obtained 178g. (62 percent of theory) of the title compound, m.p. 179.5°-181.5°C.

The following compounds are typical of those prepared using the method of the foregoing example: m-propionamido-2,2-dimethyl valeranilide, m-propionamido-2 ethyl butyranilide, m-propionamido pivalanilide, and m-pivalamino-2-2-dimethyl valeranilide.

The following is a table of the compounds which are prepared according to the aforedescribed procedures. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

                                      Table I                                      __________________________________________________________________________     Compound                                                                       Number                                                                               X Y R.sub.1      R.sub.2     R.sub.3                                                                           R.sub.4                                                                          Z   m.p. °C.                    __________________________________________________________________________     1     O O C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                            H  H      174-175                           2     O O furyl        furyl       H  H     191-194                            3     O O CH.sub.3     CH.sub.3    H  H     186-188                            4     O O CH.sub.3     C.sub.2 H.sub.5                                                                            H  H     239-243                            5     O O CH.sub.3     i-C.sub.3 H.sub.7                                                                          H  H     165-167                            6     O O n-C.sub.3 H.sub.7                                                                           n-C.sub.3 H.sub.7                                                                          H  H     142.5-143                          7     O O i-C.sub.3 H.sub.7                                                                           i-C.sub.3 H.sub.7                                                                          H  H     205-206                            8     O O C.sub.2 H.sub.5                                                                             CCl.sub.3   H  H     159-161                            9     O O H            H           H  H     152-154                            10    O O C.sub.2 H.sub.5                                                                             CH.sub.2 Cl H  H     164-167                            11    O O C.sub. 2 H.sub.5                                                                            CF.sub.3    H  H     196-197                            12    O O C.sub.2 H.sub.5                                                                             C.sub.3 H.sub.7                                                                            H  H     156-157                            13    O O C.sub.2 H.sub.5                                                                             i-C.sub.3 H.sub.7                                                                          H  H     174-175.5                          14    O O C.sub.2 H.sub.5                                                                             cyclopropyl H  H     186-188                            15    O O C.sub.2 H.sub.5                                                                             i-C.sub.4 H.sub.9                                                                          H  H     130-131                            16    O O C.sub.2 H.sub.5                                                                             n-C.sub.5 H.sub.11                                                                         H  H     173-178                            17    O O CH.sub.2 Cl  CH.sub.2 Cl H  H     211-212                            18    O O CHCl.sub.2   CHCl.sub.2  H  H     158-160                            19    O O CH.sub.2 CH.sub.2 Cl                                                                        CH.sub.2 CH.sub.2 Cl                                                                       H  H     160-163                            20    O O CH=CH.sub.2  CH=CH.sub.2 H  H     167-170                            21    O O CH=CHCH.sub.3                                                                               CH=CHCH.sub.3                                                                              H  H     215-217.5                          22    O O cyclopropyl  cyclopropyl H  H     217-221                            23    O O i-C.sub.4 H.sub.9                                                                           i-C.sub.4 H.sub.9                                                                          H  H     226-230                            24    O O n-C.sub.5 H.sub.11                                                                          n-C.sub.5 H.sub.11                                                                         H  H     122-125                            25    O O n-C.sub.6 H.sub.13                                                                          n-C.sub.6 H.sub.13                                                                         H  H     109-113                            26    O O cyclohexyl   cyclohexyl  H  H     210-212.5                          27    O O benzyl       benzyl      H  H     194-197                            28    O O CCl.sub.3    CCl.sub.3   H  H     204-207                            29    O O C(CH.sub.3).sub.2 Br                                                                        C(CH.sub.3).sub.2 Br                                                                       H  H     126-128                            30    O O t-C.sub.4 H.sub.9                                                                           t-C.sub.4 H.sub.9                                                                          H  H     188-189                            31    O O CH(C.sub.2 H.sub.5).sub.2                                                                   CH(C.sub.2 H.sub.5).sub.2                                                                  H  H     148-151                            32    O O phenyl       phenyl      H  H     234-237.5                          33    O O 3-NO.sub.2 --phenyl                                                                         3-NO.sub.2 --phenyl                                                                        H  H     250-255                            34    O O C.sub.2 H.sub.5                                                                             CHCl.sub.2  H  H     159-163                            35    O O CH=CH.sub.2  C.sub.2 H.sub.5                                                                            H  H     165-166.5                          36    O O C.sub.2 H.sub.5                                                                             CH.sub.2 CH.sub.2 Cl                                                                       H  H     139-142                            37    O O C.sub.2 H.sub.5                                                                             CH=CHCH.sub.3                                                                              H  H     183-186                            38    O O C.sub.2 H.sub.5                                                                             C(CH.sub.3).sub.2 Br                                                                       H  H     165-167                            39    O O C.sub.2 H.sub.5                                                                             n-C.sub.6 H.sub.13                                                                         H  H     256-260                            40    O O C.sub.2 H.sub.5                                                                             furyl       H  H     151-152.5                          41    O O C.sub.2 H.sub.5                                                                             cyclohexyl  H  H     300-304                            42    O O C.sub.2 H.sub.5                                                                             phenyl      H  H     210-213                            43    O O C.sub.2 H.sub.5                                                                             3-NO.sub.2 --phenyl                                                                        H  H     198-201                            44    O O C.sub.2 H.sub.5                                                                             benzyl      H  H     129-130                            45    O O i-C.sub.3 H.sub.7                                                                           cyclopropyl H  H     184-187                            46    O O i-C.sub.3 H.sub.7                                                                           CH=CH.sub.2 H  H     186-190                            47    O O i-C.sub.3 H.sub.7                                                                           n-C.sub.4 H.sub.9                                                                          H  H     124-126                            48    O O i-C.sub.3 H.sub.7                                                                           i-C.sub.4 H.sub.9                                                                          H  H     141-143                            49    O O i-C.sub.3 H.sub.7                                                                           furyl       H  H     152-154                            50    O O i-C.sub.3 H.sub.7                                                                           cyclohexyl  H  H     142-145                            51    O O i-C.sub.3 H.sub.7                                                                           phenyl      H  H     152-153                            52    O O i-C.sub.3 H.sub.7                                                                           3-NO.sub.2 --phenyl                                                                        H  H     156- 161                           53    O O CHClCH.sub.3 CHClCH.sub.3                                                                               H  H     169.5-173                          54    O O C(CH.sub.3)=CH.sub.2                                                                        C(CH.sub.3)=CH.sub.2                                                                       H  H     139-141                            55    O O C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                           C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     96-100                             56    O O CHClCH.sub.3 C.sub.2 H.sub.5                                                                            H  H     164-166                            57    O O C.sub.2 H.sub.5                                                                             C(CH.sub.3)=CH.sub.2                                                                       H  H     154-157                            58    O O i-C.sub.3 H.sub.7                                                                           CH.sub.2 Cl H  H     205-209                            59    O O i-C.sub.3 H.sub.7                                                                           CHCl.sub.2  H  H     178-180.5                          60    O O i-C.sub.3 H.sub.7                                                                           CCl.sub.3   H  H     160-162                            61    O O i-C.sub.3 H.sub.7                                                                           CHClCH.sub.3                                                                               H  H     168-172                            62    O O i-C.sub.3 H.sub.7                                                                           CH.sub.2 CH.sub.2 Cl                                                                       H  H     179-183                            63    O O i-C.sub.3 H.sub.7                                                                           CH=CHCH.sub.3                                                                              H  H     157-160                            64    O O i-C.sub.3 H.sub.7                                                                           C(CH.sub.3)=CH.sub.2                                                                       H  H     156-159                            65    O O i-C.sub.3 H.sub.7                                                                           n-C.sub.3 H.sub.7                                                                          H  H     146-148.5                          66    O O i-C.sub.3 H.sub.7                                                                           C(CH.sub.3).sub.2 Br                                                                       H  H     151-153                            67    O O i-C.sub.3 H.sub.7                                                                           n-C.sub.5 H.sub.11                                                                         H  H     122-126                            68    O O i-C.sub.3 H.sub.7                                                                           CH(C.sub.2 H.sub.5).sub.2                                                                  H  H     157-158                            69    O O i-C.sub.3 H.sub.7                                                                           n-C.sub.6 H.sub.13                                                                         H  H     114-116                            70    O O i-C.sub.3 H.sub.7                                                                           benzyl      H  H     164-167                            71    O O CF.sub.3     CF.sub.3    H  H     207-211                            72    O O CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.2 H.sub.5                                                                            H  H     177-179                            73    O O 2,4-diCl--phenyl                                                                            C.sub.2 H.sub.5                                                                            H  H     210-212                            74    O O 3,4-diCl--phenyl                                                                            C.sub.2 H.sub.5                                                                            H  H     175-177                            75    O O 4-NO.sub.2 --phenyl                                                                         C.sub.2 H.sub.5                                                                            H  H     227-230                            76    O O CH.sub.2 C(CH.sub.3).sub.3                                                                  i-C.sub.3 H.sub.7                                                                          H  H     151-153                            77    O O 2,4-diCl--phenyl                                                                            i-C.sub.3 H.sub.7                                                                          H  H     186-188                            78    O O 3,4-diCl--phenyl                                                                            i-C.sub.3 H.sub.7                                                                          H  H     189-191                            79    O O C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                           C.sub.2 H.sub.5                                                                            H  H     112-115                            80    O O CH(C.sub.2 H.sub.5)                                                                         C.sub.2 H.sub.5                                                                            H  H     153-157                            81    O O t-C.sub.4 H.sub.9                                                                           C.sub.2 H.sub.5                                                                            H  H     177-179                            82    O O CCl.sub.3    t-C.sub.4 H.sub.9                                                                          H  H     169-173                            83    O O C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                           t-C.sub.4 H.sub.9                                                                          H  H     119-120                            84    O O CF.sub.3     t-C.sub.4 H.sub.9                                                                          H  H     >300                               85    O O C(CH.sub.3).sub.2 C.sub.6 H.sub.13                                                          t-C.sub.4 H.sub.9                                                                          H  H     95-101                             86    O O C(CH.sub.3).sub.2 C.sub.6 H.sub.13                                                          C(CH.sub.3).sub.2 C.sub.6 H.sub.13                                                         H  H     94-98                              87    O O CCl.sub.2 CH.sub.3                                                                          CCl.sub.2 CH.sub.3                                                                         H  H     135.5-137.5                        88    O O CCl.sub.2 CH.sub.3                                                                          C.sub.2 H.sub.5                                                                            H  H     163-165                            89    O O CH.sub.2 C(CH.sub.3).sub.3                                                                  CH.sub.2 C(CH.sub.3).sub.3                                                                 H  H     187-190.5                          90    O O CCl.sub.3    CH.sub.2 C(CH.sub.3).sub.3                                                                 H  H     176-180                            91    O O CCl.sub.3    CH.sub.2 C(CH.sub.3).sub.3                                                                 H  H     177-180                            92    O O CF.sub.3     CH.sub.2 C(CH.sub.3).sub.3                                                                 H  H     200-201                            93    O O CCl.sub.2 CH.sub.3                                                                          CH.sub.2 C(CH.sub.3).sub.3                                                                 H  H     155.5-159                          94    O O C(CH.sub.3).sub.3                                                                           CH.sub.2 C(CH.sub.3).sub.3                                                                 H  H     184-185                            95    O O C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                           CH.sub.2 C(CH.sub.3).sub.3                                                                 H  H     105-110                            96    O O C(CH.sub.3).sub.2                                                                           C.sub.3 H.sub.7                                                                            H  H     133-134                            97    O O CF.sub.3     C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     117-120                            98    O O CCl.sub.3    C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     119-122                            99    O O C(CH.sub.3).sub.2 Br                                                                        C.sub.2 H.sub.5                                                                            H  H     144-147                            100   O O CH=C(CH.sub.3).sub.2                                                                        C.sub.2 H.sub.5                                                                            H  H     66-72                              101   O O CH--C.sub.2 H.sub.5 ).sub.2                                                                 C.sub.2 H.sub.5                                                                            H  H     155.5-156                          102   O O CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        C.sub.2 H.sub.5                                                                            H  H     127-130                            103   O O CH.sub.2 OCH.sub.3                                                                          CH.sub.2 C(CH.sub.3).sub.3                                                                 H  H     n.sub.D.sup.30 =1.5441             104   O O CH=C(CH.sub.3).sub.2                                                                        CH=C(CH.sub.3).sub.2                                                                       H  H     (glass)                            105   O O CH=C(CH.sub.3).sub.2                                                                        C(CH.sub.3).sub.3                                                                          H  H     112-117                            106   O O CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        C(CH.sub.3).sub.3                                                                          H  H     109-112                            107   O O CH=C(CH.sub.3).sub.2                                                                        C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     (glass)                            108   O O CH.sub.2 CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                             C.sub.2 H.sub.5                                                                            H  H     108-111                            109   O O CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                       H  H     150-152                            110   O O CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        C(CH.sub.3).sub.2 H.sub.7                                                                  H  H     114-116                            111   O O CH.sub.2 CH(CH.sub. 3)CH.sub.2 C(CH.sub.3).sub.3                                            C(CH.sub.3).sub.3                                                                          H  H     48-51                              112   O O CH.sub.2 CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                             C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     (glass)                            113   O O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 C.sub.2 H.sub.5                                                                            H  H     150-151                            114   O O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 CH(CH.sub.3)C.sub.2 H.sub.5                                                                H  H     159-161                            115   O O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 C(CH.sub.3).sub.3                                                                          H  H     169-171                            116   O O CH.sub.2 C(CH.sub.3).sub.3                                                                  CH(CH.sub.3)C.sub.2 H.sub.5                                                                H  H     146-149                            117   O O CF.sub.3     CH(CH.sub.3)C.sub.2 H.sub.5                                                                H  H     157-158                            118   O O 2-Cl--phenyl C.sub.2 H.sub.5                                                                            H  H     143.5-144.5                        119   O O 4-Cl--phenyl C.sub.2 H.sub.5                                                                            H  H     223-224.5                          120   O O 2-CH.sub.3 O--phenyl                                                                        C.sub.2 H.sub.5                                                                            H  H     124-125                            121   O O 4-CH.sub.3 O--phenyl                                                                        C.sub.2 H.sub.5                                                                            H  H     223-224                            122   O O 4-CH.sub.3 --phenyl                                                                         C.sub. 2 H.sub.5                                                                           H  H     211-212                            123   O O 4-Cl--phenyl C(CH.sub.3).sub.3                                                                          H  H     191-195                            124   O O benzyl       C(CH.sub.3).sub.3                                                                          H  H     164-165                            125   O O benzyl       CH(CH.sub.3)C.sub.2 H.sub.5                                                                H  H     161-163                            126   O O benzyl       CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     149.5-151                          127   O O benzyl       C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     142-143.5                          128   O O styryl       C.sub.2 H.sub.5                                                                            H  H     160-163                            129   O O --CH.sub.2 CH.sub.3                                                                         CH(CH.sub.3).sub.2                                                                         H  H 4'-Cl                                                                              161-162                            130   O O C(CH.sub.3).sub.3                                                                           CH(CH.sub.3).sub.2                                                                         H  H 4'-Cl                                                                              176.5-178.5                        131   O O CH.sub.2 C(CH.sub.3).sub.3                                                                  CH(CH.sub.3).sub.2                                                                         H  H 4'-Cl                                                                              194-194.5                          132   O O CCl.sub.3    CH(CH.sub.3).sub.2                                                                         H  H 4'-Cl                                                                              156-158                            133   O O benzyl       CH(CH.sub.3).sub.2                                                                         H  H 4'-Cl                                                                              211-212                            134   O O C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                   H     132-133                            135   O O CH.sub.2 C(CH.sub.3).sub.3                                                                  C.sub.2 H.sub.5                                                                            C.sub.2 H.sub.5                                                                   H     178.5-180                          136   O O CH.sub.2 OCH.sub.3                                                                          C(CH.sub.3).sub.3                                                                          H  H     108-109                            137   O O CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        C(CH.sub.3).sub.3                                                                          H  H     115-116                            138   O O CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                       H  H     151-153                            139   O O CH.sub.2 CH.sub.2 CH(CH.sub.3).sub.2                                                        C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     121-123                            140   O O CH.sub.2 CH.sub.2 --phenyl                                                                  CH.sub.2 C(CH.sub.3).sub.3                                                                 H  H     101-107                            141   O O C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5 C(CH.sub.3).sub.3                                                          H  H     178-179                            142   O O CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                         CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     75-77                              143   O O CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                         CH.sub.2 C(CH.sub.3).sub.3                                                                 H  H     184-185                            144   O O CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                         CH.sub.2 CH.sub. 2 C(CH.sub.3).sub.3                                                       H  H     216-218                            145   O O CH.sub.2 CH.sub.2 C(CH.sub.3).sub.3                                                         C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     151-153                            146   O O C(CH.sub.3).sub.2 CH.sub.2 Cl                                                               C(CH.sub.3).sub.2 CH.sub.2 Cl                                                              H  H     145-150                            147   O O C(CH.sub.3).sub.2 CH.sub.2 Cl                                                               C.sub.2 H.sub.5                                                                            H  H     161-164                            148   O O C(CH.sub.3).sub.2 CH.sub.2 Cl                                                               C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     110-112                            149   O O C.sub.2 H.sub.5                                                                             CH.sub.2 O-2,4diCl--phenyl                                                                 H  H     206-207                            150   O O CH.sub.2 CH=CH.sub.2                                                                        C.sub.2 H.sub.5                                                                            H  H     135-139                            151   O O CH.sub.2 CH=CH.sub.2                                                                        CH.sub.2 CH=CH.sub.2                                                                       H  H     99-108                             152   O O C(CH.sub.3)=CH.sub.2                                                                        C(CH.sub.3).sub.3                                                                          H  H     159-166                            153   O O cyclopropyl  C(CH.sub.3).sub.3                                                                          H  H     176-178                            154   O O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                            H  H     147-149                            155   O O C(CH.sub.3 )C.sub.2 H.sub.5                                                                 C.sub.2 H.sub.5                                                                            H  H     141-144                            156   O O C.sub.3 H.sub.7 -n                                                                          C(CH.sub.3).sub.3                                                                          H  H     172-175                            157   O O CH.sub.2 CH(CH.sub.3).sub.2                                                                 C(CH.sub.3).sub.3                                                                          H  H     164.5-167                          158   O O n-C.sub.4 H.sub.9                                                                           C(CH.sub.3).sub.3                                                                          H  H     125-127                            159   O O C(CH.sub.3).sub.2 CH.sub.2 Cl                                                               C(CH.sub.3).sub.3                                                                          H  H     151-153                            160   O O CH.sub.2 CH.sub.2 cyclopentyl                                                               C.sub.2 H.sub.5                                                                            H  H     165-166                            161   O O CH(C.sub.2 H.sub.5).sub.2                                                                   C(CH.sub.3).sub.3                                                                          H  H     168-170                            162   O O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 C(CH.sub.3).sub.3                                                                          H  H     145-148                            163   O O CH(CH.sub.3).sub.2                                                                          C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     115-120                            164   O O CH.sub.2 CH.sub.2 cyclohexyl                                                                C.sub.2 H.sub.5                                                                            H  H     154-155                            165   O O cyclohexyl   C(CH.sub.3).sub.3                                                                          H  H     187-188                            166   O O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     111-115                            167   O O C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                           C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                          H  H     156-158                            168   O O pinonoyl     C.sub.2 H.sub.5                                                                            H  H     glass                              169   O O C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                           C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     120.5-123                          170   O O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     glass                              171   O O cyclohexyl   cyclohexyl  H  H     217-219                            172   O O cyclohexyl   C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     153.5-157                          173   O O 3-4-diCl--phenyl                                                                            C(CH.sub.3).sub.3                                                                          H  H     187-191                            174   O O CH.sub.2 O-2,4-diCl--phenyl                                                                 C(CH.sub.3).sub.3                                                                          H  H     163-165                            175   O O 3,4-diCl--phenyl                                                                            C(CH.sub.3)C.sub.3 H.sub.7                                                                 H  H     107-114                            176   O O 2,4-diCl--phenyl                                                                            C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     153-157                            177   O O CH.sub.2 O-2,4-diCl--phenyl                                                                 C(CH.sub.3)C.sub.3 H.sub.7                                                                 H  H     126-129                            178   O O C(i-C.sub.3 H.sub.7).sub.2 CH.sub.3                                                         C.sub.2 H.sub.5                                                                            H  H     n.sub.D.sup. 30 1.5225             179   O O CH=CHCH.sub.3                                                                               C(CH.sub.3).sub.3                                                                          H  H     67-69                              180   O O CH.sub.2 CH=CH.sub.2                                                                        C(CH.sub.3).sub.3                                                                          H  H     159-161                            181   O O CH.sub.2 CH.sub.2 cyclopentyl                                                               C(CH.sub.3).sub.3                                                                          H  H     142-143                            182   O O CH.sub.2 CH.sub.2 cyclohexyl                                                                C(CH.sub.3).sub.3                                                                          H  H     141.5-143                          183   O O 3'-pinonyl   C(CH.sub.3).sub.3                                                                          H  H     61-67                              184   O O 2,4-diCl--phenyl                                                                            C(CH.sub.3).sub.3                                                                          H  H     182-184                            185   O O C(i-C.sub.3 H.sub.7).sub.2 CH.sub.3                                                         C(CH.sub.3).sub.3                                                                          H  H     62-66                              186   O O CCl.sub.3    CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     121-126                            187   O O CF.sub.3     CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     139-146                            188   O O CH(CH.sub.3).sub.2                                                                          CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     156-157                            189   O O CH(CH.sub.3)C.sub.2 H.sub.5                                                                 CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     145-147                            190   O O C(CH.sub.3).sub.2 CH.sub.2 Cl                                                               CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     n.sub.D.sup.30 1.5145              191   O O CH.sub.2 C(CH.sub.3).sub.3                                                                  CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     n.sub.D.sup.30 1.5078              192   O O CH.sub.2 CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                             CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     n.sub.D.sup.30 1.5020              193   O O CH.sub.2 O-2,4-diCl--phenyl                                                                 CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     182.184                            194   O O C(CH.sub.3).sub.3                                                                           C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                          H  H     131-134.5                          195   O O CH.sub.2 C(CH.sub.3).sub.3                                                                  C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                          H  H     133-135                            196   O O CH.sub.2 CH(CH.sub.3)CH.sub.2 C(CH.sub.3).sub.3                                             C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                          H  H     57-62                              197   O O CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                        C.sub.2 H.sub.5                                                                            H  H     123-126                            198   O O CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                        C(CH.sub.3).sub.3                                                                          H  H     134-136                            199   O O CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                        CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     107-108                            200   O O CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                        C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     100-103                            201   O O CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                        CH.sub.2 CH(CH.sub.3)C.sub.2 H.sub.5                                                       H  H     132-134                            202   O O CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                          C.sub.2 H.sub.5                                                                            H  H     126-129                            203   O O CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                          CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                         H  H     53-70                              204   O O CH.sub.2 C(CH.sub.3).sub.3                                                                  CH(CH.sub.3)CH.sub.3                                                                       H  H     189-192                            205   O O C.sub.2 H.sub.5                                                                             C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                          H  H     134-137                            206   O O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 C(C.sub.2 H.sub.5).sub.2 CH.sub.3                                                          H  H     45-48                              207   O O CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                  C.sub.2 H.sub.5                                                                            H  H     174-175                            208   O O CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                  C(CH.sub.3).sub.3                                                                          H  H     156-157                            209   O O CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                          C(CH.sub.3).sub.3                                                                          H  H     132- 134                           210   O O CH(C.sub.2 H.sub.5)C.sub.3 H.sub.7                                                          CH(CH.sub.3 C.sub.3 H.sub.7                                                                H  H     108-112                            211   O O CH(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                          C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     119-121                            212   O O CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                  CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     135-136                            213   O O CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                  C(CH.sub.3)C.sub.3 H.sub.7                                                                 H  H     108-110                            214   O O CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                  CH.sub.2 C(CH.sub.3).sub.2 C.sub.2 H.sub.5                                                 H  H     175-178                            215   O O C.sub.2 F.sub.5                                                                             C.sub.2 H.sub.5                                                                            H  H     172-175                            216   O O C.sub.2 F.sub.5                                                                             C(CH.sub.3).sub.3                                                                          H  H     187-190                            217   O O C.sub.2 F.sub.5                                                                             CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     126-128                            218   O O C.sub.2 F.sub.5                                                                             C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     112-114                            219   O O CCl.sub.2 CF.sub.3                                                                          C.sub.2 H.sub.5                                                                            H  H     141-143                            220   O O 2-CH.sub.3 --phenyl                                                                         C(CH.sub.3).sub.3                                                                          H  H     185-186.5                          221   O O 3-CH.sub.3 --phenyl                                                                         C(CH.sub.3).sub.3                                                                          H  H     163-164                            222   O O 4-CH.sub.3 --phenyl                                                                         C(CH.sub.3).sub.3                                                                          H  H     206-207                            223   O O 2-CH.sub.3 --phenyl                                                                         CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     172-174                            224   O O 3-CH.sub.3 --phenyl                                                                         CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     68-72                              225   O O 4-CH.sub.3 --phenyl                                                                         CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     122-124                            226   O O 2-CH.sub.3 --phenyl                                                                         C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     154-155                            227   O O 3-CH.sub.3 --phenyl                                                                         C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     129-130                            228   O O 4-CH.sub.3 --phenyl                                                                         C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     146-148                            229   O O 2-Cl--phenyl C(CH.sub.3).sub.3                                                                          H  H     185-187                            230   O O 3-Cl--phenyl C(CH.sub.3).sub.3                                                                          H  H     193-194                            231   O O 2-Cl--phenyl CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     154-156                            232   O O 3-Cl--phenyl CH(CH.sub.3 )C.sub.3 H.sub.7                                                               H  H     118-120                            233   O O 4-Cl--phenyl CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     131-133                            234   O O 2-Cl--phenyl C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     128-130                            235   O O 3-Cl--phenyl C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     132-133                            236   O O 4-Cl--phenyl C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     135-137                            237   O O 2-F--phenyl  C.sub.2 H.sub.5                                                                            H  H     186-187                            238   O O 4-F--phenyl  C.sub.2 H.sub.5                                                                            H  H     205-206                            239   O O 2-F--phenyl  C(CH.sub.3).sub.3                                                                          H  H     123-126                            240   O O 4-F--phenyl  C(CH.sub.3).sub.3                                                                          H  H     195-196                            241   O O 2-F--phenyl  CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     129-131                            242   O O 4-F--phenyl  CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H     141-143                            243   O O 2-F--phenyl  C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     114-115                            244   O O 4-F--phenyl  C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H     147-149                            245   O O CH(C.sub.2 H.sub.5).sub.2                                                                   CH(CH.sub. 3)C.sub.3 H.sub.7                                                               H  H     157-159                            246   O O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H 3-Cl                                                                               63-66                              247   O O C.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                            H  H 2-CH.sub.3                                                                         266-267                            248   O O i-C.sub.3 H.sub.7                                                                           i-C.sub.3 H.sub.7                                                                          H  H 2-CH.sub.3                                                                         295-296                            249   O O t-C.sub.4 H.sub.9                                                                           t-C.sub.4 H.sub.9                                                                          H  H 2-CH.sub.3                                                                         260-261                            250   O O CH(CH.sub.3)C.sub.3 H.sub.7                                                                 CH(CH.sub.3)C.sub.3 H.sub.7                                                                H  H 2-CH.sub.3                                                                         245-246                            251   O O C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                           C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                          H  H 2-CH.sub.3                                                                         176-177                            __________________________________________________________________________

Other examples of compounds falling within the generic formulas presented herein, which are preparable by the above-described procedures and which may be formulated into herbicidal compositions and applied as herein illustrated are:

    X Y R.sub.1   R.sub.2  R.sub.3                                                                            R.sub.4                                                                            Z                                               __________________________________________________________________________     O S H         H        H   H                                                   O S C.sub.2 H.sub.5                                                                          H        H   H                                                   O S C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                         H   H                                                   O S C.sub.2 H.sub.5                                                                          cyclopropyl                                                                             H   H                                                   O S CH.sub.2 Cl                                                                              CH.sub.2 Cl                                                                             H   H                                                   O S cyclopropyl                                                                              n-C.sub.5 H.sub.11                                                                      H   H                                                   O S CH=CHCH.sub.3                                                                            C.sub.2 H.sub.5                                                                         H   H                                                   O S furyl     furyl    H   H                                                   O S CCl.sub.3 C.sub.2 H.sub.5                                                                         H   H                                                   O S phenyl    phenyl   H   H                                                   O S cyclohexyl                                                                               cyclohexyl                                                                              H   H                                                   O S benzyl    C.sub.2 H.sub.5                                                                         H   H                                                   O S 2,4-diCl-phenyl                                                                          C.sub.2 H.sub.5                                                                         H   H                                                   O S 4-NO.sub.2 -phenyl                                                                       C.sub.2 H.sub.5                                                                         H   H                                                   O S 3,4-diCl-phenyl                                                                          i-C.sub.3 H.sub.7                                                                       H   H                                                   O S C.sub.2 H.sub.5                                                                          CF.sub.3 H   H                                                   O S t-C.sub.4 H.sub.9                                                                        t-C.sub.4 H.sub.9                                                                       H   H                                                   O S phenyl    phenyl   H   H                                                   O S cyclohexyl                                                                               cyclohexyl                                                                              H   H   5'-Cl                                           O S C.sub.2 H.sub.5                                                                          3-NO.sub.2 --phenyl                                                                     H   H                                                   O O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       H   H   5'-Cl                                           O O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       H   H   5'-Br                                           O O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       H   H   5'-F                                            O O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       H   H   5'-C.sub.2 H.sub.5                              O O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       H   H   5'-NO.sub.2                                     O O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       H   H   5'-CF.sub.3                                     O O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       H   CH.sub.3                                            O S C.sub.2 H.sub.5                                                                          CH(C.sub.2 H.sub.5)2                                                                    H   CH.sub.3                                                                           5'-Cl                                           O S C.sub.2 H.sub.5                                                                          phenyl   H   CH.sub.3                                                                           5'-NO.sub.2                                     O O CH.sub.2 C(CH.sub.3).sub.3                                                               C.sub.2 H.sub.5                                                                         CH.sub.3                                                                           CH.sub.3                                            O O CH.sub.2 C(CH.sub.3).sub.3                                                               C.sub.2 H.sub.5                                                                         CH.sub.3                                                                           H   5'-Cl                                           O O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                           H   5'-CF.sub.3                                     O O C(CH.sub.3).sub.2 C.sub.3 H.sub.7                                                        C.sub. 2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           5'-NO.sub.2                                     O S C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                           CH.sub.3                                                                           5'-CH.sub.3                                     O O H         H        H   H   5'-NH.sub.2                                     O O C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                         H   H   5'NH.sub.2                                      O O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                           CH.sub.3                                                                           5'-NH.sub.2                                     O S H         H        CH.sub.3                                                                           CH.sub.3                                                                           5'-OCH.sub.3                                    O S C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                         H   H   5'-OC.sub.2 H.sub.5                             S O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                           CH.sub.3                                                                           5'-OCH.sub.3                                    S O C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                       H   CH.sub.3                                                                           5'-NH.sub.2                                     S O CH.sub.3  i-C.sub.3 H.sub.7                                                                       H   H   5'-OCH.sub.3                                    S S C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                         CH.sub.3                                                                           CH.sub.3                                                                           5'-OCH.sub.3                                    S S C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                         H   H   5'-NH.sub.2                                     O O CH.sub.2 OC.sub.2 H.sub.5                                                                C.sub.2 H.sub.5                                                                         H   H                                                   O O C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                         i-C.sub.3 H.sub.7                                                                       CH.sub.3                                                                           H                                                   __________________________________________________________________________

Pre-emergence herbicide test. On the day preceding treatment, seeds of seven different weed species are planted in individual rows using one species per row across the width of the flat. The seeds used are hairy crabgrass (Digitaria sanguinalis (L.) Scop.), yellow foxtail (Setaria glauca (L.) Beauv.), watergrass (Echinochloa crusgalli (L.) Beauv.), California red oat (Avena sativa (L.)), redroot pigweed (Amaranthus retroflexus (L.), Indian Mustard (Brassica juncea (L.) Coss.) and curly dock (Rumex crispus (L.). Ample seeds are planted to give about 20 to 50 seedlings per row, after emergence, depending on the size of the plants. The flats are watered after planting. The spraying solution is prepared by dissolving 50 mg. of the test compound in 3 ml. of a solvent, such as acetone, containing 1% Tween 20 (polyoxy-ethylene sorbitan monolaurate.) The following day, each flat is sprayed at the rate of 20 pounds of the candidate compound per 80 gallons of solution per acre. An atomizer is used to spray the solution on soil surface. The flats are placed in a greenhouse at 80°F. and watered regularly. Two weeks later, the degree of weed control is determined by comparing the amount of germination and growth of each weed in the treated flats with weeds in several untreated control flats.

The rating system is as follows:

    - =    no significant injury (0-15 percent control)                            + =    slight injury (25-35 percent control)                                   ++ =   moderate injury (55-65 percent control)                                 +++ =  severe injury or death (85-100 percent control)                    

An activity index is used to represent the total activity on all seven weed species. It is the sum of the number of plus marks, so that an activity index of 21 represents complete control of all seven weeds. The results of this test are reported in Table II.

Post-emergence Herbicide Test

Seeds of five weed species including hairy crabgrass, watergrass, wild oats, Indian mustard, and curly dock and one crop pinto beans (Phaseolus vulgaris), are planted in flats as described above for pre-emergence screening. The flats are placed in the greenhouse at 72°-85°F. and watered daily with a sprinkler. About 10 to 14 days after planting when the primary leaves of the bean plant are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 50 mg. of the test compound, dissolving it in 5 ml. of acetone containing 1 percent Tween 20 (polyoxy-ethylene sorbitan monolaurate) and then adding 5 ml. of water. The solution is sprayed on the foliage using an atomizer. The spray concentration is 0.5% and the rate would be approximately 20 lb/acre if all of the spray were retained on the plant and the soil, but some spray is lost so it is estimated that the application rate is approximately 12.5 lb/acre.

Beans are used to detect defoliants and plant growth regulators. The beans are trimmed to two or three plants per flat by cutting off the excess weaker plants several days before treatment. The treated plants are placed back in the greenhouse and care is taken to avoid sprinkling the treated foliage with water for three days after treatment. Water is applied to the soil by means of a slow stream from a watering hose taking care not to wet the foliage.

Injury rates are recorded 14 days after treatment. The rating system is the same as described above for the pre-emergence test where (-), (+), (++), and (+++) are used for the different rates of injury and control. The injury symptoms are also recorded. The maximum activity index for complete control of all the species in the post-emergence screening test is 18 which represents the sum of the plus marks obtained with the six plant species used in the test. The herbicide activity index is shown in Table II.

                  TABLE II                                                         ______________________________________                                         HERBICIDAL ACTIVITY ** - SCREENING RESULTS                                     Compound                                                                       Number      Pre-emergence  Post-emergence                                      ______________________________________                                         1           12             15                                                  2           2              12                                                  3           7              3                                                   4           1              0                                                   5           0              5                                                   6           9              5                                                   7           18             15                                                  8           15             18                                                  9           0              7                                                   10          0              8                                                   11          19             18                                                  12          11             16                                                  13          20             18                                                  14          17             15                                                  15          14             18                                                  16          0              13                                                  17          1              8                                                   18          0              9                                                   19          0              7                                                   20          0              10                                                  21          12             16                                                  22          12             15                                                  23          6              13                                                  24          6              12                                                  25          4              8                                                   26          8              9                                                   27          11             16                                                  28          9              14                                                  29          17             15                                                  30          21             17                                                  31          2              11                                                  32          0              8                                                   33          0              9                                                   34          9              16                                                  35          2              9                                                   36          9              15                                                  37          6              14                                                  38          20             18                                                  39          6              12                                                  40          11             12                                                  41          5              14                                                  42          10             12                                                  43          9              12                                                  44          8              18                                                  45          18             16                                                  46          8              11                                                  47          8              12                                                  48          6              12                                                  49          16             18                                                  50          5              12                                                  51          5              11                                                  52          6              12                                                  53          6              0                                                   54          12             12                                                  55          21             18                                                  56          19             17                                                  57          6              8                                                   58          0              2                                                   59          10             9                                                   60          21             18                                                  61          15             16                                                  62          7              12                                                  63          16             16                                                  64          14             15                                                  65          3              10                                                  66          20             17                                                  67          8              8                                                   68          21             18                                                  69          0              11                                                  70          14             15                                                  71          10             11                                                  72          21             18                                                  73          11             12                                                  74          12             11                                                  76          20             18                                                  77          12             15                                                  78          3              11                                                  79          21             18                                                  80          18             18                                                  81          19             18                                                  82          17             16                                                  83          18             18                                                  84          7              12                                                  85          6              7                                                   86          0              2                                                   87          19             16                                                  88          21             18                                                  89          9              12                                                  90          0              3                                                   91          11             16                                                  92          4              10                                                  93          8              18                                                  94          20             18                                                  95          19             18                                                  96          18             18                                                  97          11             18                                                  98          6              14                                                  99          19             18                                                  100         13             18                                                  101         19             18                                                  102         6              15                                                  103         12             18                                                  104         19             18                                                  105         20             18                                                  106         14             17                                                  107         17             18                                                  108         11             18                                                  109         6              12                                                  110         12             17                                                  111         12             18                                                  112         9              14                                                  113         21             18                                                  114         19             18                                                  115         20             18                                                  116         21             18                                                  117         5              18                                                  118         11             17                                                  119         9              14                                                  120         5              14                                                  121         0              1                                                   122         0              12                                                  123         0              12                                                  124         17             18                                                  125         10             18                                                  126         9              18                                                  127         15             18                                                  128         3              17                                                  129         9              16                                                  130         7              9                                                   131         7              11                                                  132         16             15                                                  133         8              9                                                   134         6              14                                                  135         6              11                                                  136         12             13                                                  137         14             15                                                  138         2              13                                                  139         14             14                                                  140         0              7                                                   141         14             18                                                  142         12             16                                                  143         5              12                                                  144         0              2                                                   145         6              12                                                  146         3              4                                                   147         21             18                                                  148         21             17                                                  149         8              12                                                  150         10             17                                                  151         7              16                                                  152         15             17                                                  153         16             18                                                  154         18             18                                                  155         16             18                                                  156         17             19                                                  157         19             17                                                  158         11             16                                                  159         15             14                                                  160         3              11                                                  161         19             18                                                  162         21             18                                                  163         21             18                                                  164         0              8                                                   165         9              16                                                  166         18             18                                                  167         11             13                                                  168         9              15                                                  169         21             17                                                  170         20             18                                                  171         0              0                                                   172         0              14                                                  173         0              15                                                  174         17             15                                                  175         8              16                                                  176         9              14                                                  177         9              16                                                  178         9              18                                                  179         18             18                                                  180         19             18                                                  181         2              12                                                  182         0              9                                                   183         6              8                                                   184         14             12                                                  185         13             9                                                   186         14             15                                                  187         19             18                                                  188         21             16                                                  189         20             16                                                  190         21             18                                                  191         21             18                                                  192         9              12                                                  193         5              10                                                  194         18             11                                                  195         13             9                                                   196         1              4                                                   197         20             16                                                  198         21             16                                                  199         21             15                                                  200         21             16                                                  201         19             14                                                  202         21             18                                                  203         0              6                                                   204         10             11                                                  205         21             17                                                  206         21             15                                                  207         18             18                                                  208         17             15                                                  209         13             17                                                  210         13             18                                                  211         6              13                                                  212         16             14                                                  213         13             5                                                   214         0              4                                                   215         20             18                                                  216         16             18                                                  217         15             18                                                  218         16             18                                                  219         17             18                                                  220         4              11                                                  221         7              14                                                  222         0              4                                                   223         3              11                                                  224         8              12                                                  225         2              14                                                  226         7              14                                                  227         9              15                                                  228         0              10                                                  229         11             10                                                  230         6              10                                                  231         8              12                                                  232         8              12                                                  233         5              11                                                  234         9              13                                                  235         9              14                                                  236         6              12                                                  237         7              6                                                   238         11             10                                                  239         15             16                                                  240         8              9                                                   241         9              11                                                  242         8              12                                                  243         10             14                                                  244         6              11                                                  245         19             18                                                  246         0              14                                                  247         6              5                                                   248         0              5                                                   249         5              5                                                   250         3              4                                                   251         6              7                                                   ______________________________________                                    

21 = 85-100% control of all seven plant species tested pre-emergence.

18 - 85-100% control of all six plant species tested post-emergence

The compounds of the present invention are used as pre-emergence of post-emergence herbicides and are applied in a variety of ways at various concentrations. In practice, the compounds are formulated with an inert carrier, utilizing methods well-known to those skilled in the art, thereby making them suitable for application as dusts, sprays, or drenches and the like in the form and manner required. The mixtures can be dispersed in water with the aid of a wetting agent or they can be employed in organic liquid compositions, oil and water, water in oil emulsions, with or without the addition of wetting, dispersing or emulsifying agents. The amount applied depends upon the nature of the seeds or plants to be controlled and the rate of application varies from approximately 1 to approximately 50 pounds per acre. One particularly advantageous way of applying the compound is a narrow band along a row crop straddling the row. In practice, the compounds are formulated with an inert carrier utilizing methods well known to those skilled in the art, thereby making them suitable for particular application.

The phytotoxic compositions of this invention are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray-dusters. The compositions can also be applied from airplanes as a dust or a spray because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions are applied to the soil according to conventional methods and are preferably distributed in the soil to a depth of at least 1/2-inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles and these compositions can be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain other additaments, for example fertilizers, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants. Other phytotoxic compounds useful in combination with the above-described compounds include for example 2,4-dichlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid, 2 - methyl - 4-chlorophenoxyacetic acid and the salts, esters and amides thereof; triazine derivatives, such as 2,4-bis (3-methoxypropylamino)-6-methylthio-S-triazine; 2-chloro-4-ethylamino-6-isopropylamino-S-triazine, and 2-ethylamino-4-isopropylamino-6-methylmercapto-S-triazine, urea derivatives, such as 3-(3,4-dichlorophenyl)-1,1-dimethyl urea and 3-(p-chlorophenyl)-1,1-dimethyl urea and acetamides such as N,N - dially - α -chloroacetamide, N-(α-chloroacetayl)hexamethylene imine, and N,N-diethyl-a-bromacetamide and the like; benzoic acids such as 3-amino-2,5-dichlorobenzoic and; thiocarbamates, such as S-propyl dipropylthiocarbamate; S-ethyl-dipropylthiocarbamate, S-ethyl-cyclohexylethyl-thiocarbamate, S-ethyl hexahydro-1H-azepine-1-carbothioate and the like. Fertilizers useful in combination with the active ingredients include for example ammonium nitrate, urea and superphosphates. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

The concentration of a compound of the present invention, constituting an effective amount in the best mode of administration in the utility disclosed is readily determinable by those skilled in the art. Various changes and modifications are possible without departing from the spirit and scope of the invention described herein and will be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the claims. 

What is claimed is:
 1. A compound having the formula ##SPC4##in which R₂ is halogenated lower alkyl, and R₁ is alkyl.
 2. A compound according to claim 1 in which R₁ is ethyl and R₂ is 1-bromo-1-methylethyl.
 3. A compound according to claim 1 in which R₁ is isopropyl and R₂ is trichloromethyl.
 4. A compound according to claim 1 in which R₁ is isopropyl and R₂ is 1-chloroethyl.
 5. A compound according to claim 1 in which R₁ is isopropyl and R₂ is 1-bromo-1-methylethyl.
 6. A compound according to claim 1 in which R₁ is ethyl and R₂ is trifluoromethyl.
 7. A compound according to claim 1 in which R₂ is 1-bromo-iso-propyl and R₁ is ethyl.
 8. A compound according to claim 1 in which R₂ is 1,1-dichloroethyl and R₁ is ethyl.
 9. A compound according to claim 1 in which R₂ is trifluoromethyl and R₁ is 1,1-dimethylbutyl.
 10. A compound according to claim 1 in which R₂ is 1,1-dimethyl-2-chloroethyl and R₁ is ethyl.
 11. A compound according to claim 1 in which R₂ is 1,1-dimethyl-2-chloroethyl and R₁ is 1,1-dimethylbutyl.
 12. The compound having the formula ##SPC5##
 13. A compound having the formula ##SPC6##in which R₁ is lower alkenyl, R₂ is alkyl.
 14. A compound according to claim 13 in which R₁ is 2,2-dimethylvinyl, R₂ is tert-butyl.
 15. A compound according to claim 13 in which R₁ is 2,2-dimethylvinyl, R₂ is 1,1-dimethylbutyl.
 16. A compound according to claim 13 in which R₁ is 2,2-dimethylvinyl, R₂ is ethyl.
 17. A compound according to claim 13 in which R₁ is vinyl, R₂ is ethyl.
 18. A compound having the formula ##SPC7##in which R₁ is benzyl and R₂ is alkyl.
 19. A compound according to claim 18 in which R₂ is tert-butyl.
 20. A compound according to claim 18 in which R₂ is sec-butyl.
 21. A compound according to claim 18 in which R₂ is 1-methylbutyl.
 22. A compound according to claim 18 in which R₂ is 1,1-dimethylbutyl.
 23. A compound having the formula ##SPC8##in which R₁ is chlorophenyl and R₂ is alkyl.
 24. A compound according to claim 23 in which R₁ is 2-chlorophenyl and R₂ is ethyl.
 25. A compound according to claim 23 in which R₁ is 4-chlorophenyl and R₂ is ethyl.
 26. A compound according to claim 23 in which R₁ is 4-chlorophenyl and R₂ is tert-butyl.
 27. A compound having the formula ##SPC9##in which R₁ is styryl and R₂ is alkyl.
 28. A compound according to claim 27 in which R₂ is ethyl.
 29. A compound having the formula ##SPC10##in which R₁ is 2,4,4-trimethylpentyl and R₂ is 1,1-dimethylbutyl.
 30. A compound having the formula ##SPC11##in which R₁ is 1,1-dimethylbutyl, R₂ is neopentyl.
 31. A compound having the formula ##SPC12##in which R₁ is tert.-butyl and R₂ is neopentyl.
 32. A compound having the formula ##SPC13##in which R₁ is 1-methylbutyl, and R₂ is tert.-butyl.
 33. A compound having the formula ##SPC14##in which R₁ is 3,4-dichlorophenyl and R₂ is ethyl.
 34. A compound having the formula ##SPC15##in which R₁ is 2,4-dichlorophenyl and R₂ is tert.-butyl.
 35. A compound having the formula ##SPC16##in which R₁ is cyclopropyl and R₂ is tert.-butyl.
 36. Compound having the formula ##SPC17##in which R₁ and R₂ are as follows: a. R₁ is 2,2-dimethylpropyl and R₂ is isopropyl b. R₁ is isopropyl and R₂ is 1-ethylpropyl c. R₁ is isopropyl and R₂ is 1,1-dimethylbutyl d. R₁ is isopropyl and R₂ is 1-methylbutyl e. R₁ is 2-methylbutyl and R₂ is tert.-butyl f. R₁ is 1,1-dimethylbutyl and R₂ is tert.-butyl g. R₁ is tert.-butyl and R₂ is 2,2-dimethylpropyl h. R₁ is 3-methylbutyl and R₂ is tert.-butyl i. R₁ is 1-methylpropyl and R₂ is tert.-butyl j. R₁ is 2,2-dimethylpropyl and R₂ is 1-methylpropyl k. R₁ is 2,2-dimethylpropyl and R₂ is 1-methylbutyl l. R₁ is 1-methylbutyl and R₂ is 1,1-dimethylbutyl m. R₁ is 1-methylpropyl and R₂ is 1-methylbutyl n. R₁ is 2-methylbutyl and R₂ is 1-methylbutyl o. R₁ is 2,2-dimethylbutyl and R₂ is 1-methylbutyl p. R₁ is 2-methylbutyl and R₂ is 1,1-dimethylbutyl. 